Polymer compositions and use of these polymer compositions as viscosity modifiers

Abstract

The present invention relates to novel polymer compositions, to a process for their manufacturing, to the use of said polymer compositions for modifying the viscosity of aqueous compositions, and to water-borne coating compositions containing the novel polymer compositions as thickeners. The polymer compositions comprise a polymer material which is obtainable by reacting: a) a polymer P1 having at least one functional group of the formula (I), where k is an integer from 0 to 4; n is 0 or 1 p is an integer from 1 to 10, the number average of p being from 1.5 to 10; Q is a divalent moiety selected from the group consisting of O and NH; P is a p-valent hydrophilic neutral polymer radical; and R.sup.1 is as defined in the claims; with b) a succinic anhydride of the formula (II) where R is C.sub.4-C.sub.24-alkyl or C.sub.4-C.sub.24-alkenyl. ##STR00001##

Claims

1. A polymer composition comprising a polymer material which is prepared by reacting a) a polymer P1 of the formula (I): ##STR00008## with b) a succinic anhydride of the formula (II): ##STR00009## to obtain a polymer composition comprising at least one of polymers of formulae (IVa) and (IVb): ##STR00010## wherein k is an integer from 0 to 4; n is 0 or 1 p is an integer from 1 to 10, wherein a number average of p is from 1.5 to 10; Q is a divalent moiety selected from the group consisting of O and NH; P is a p-valent hydrophilic neutral polymer radical; R.sup.1 is independently selected from the group consisting of halogen, COOCH.sub.3, N(C.sub.1-C.sub.6-alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, aryloxy, aryl, heteroaryl, where aryl, hetaryl and aryloxy are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of OH, COOCH.sub.3, N(C.sub.1-C.sub.6-alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy and halogen; R.sup.2 is selected from the group consisting of NH.sub.2, NH(C.sub.1-C.sub.6-alkyl), N(C.sub.1-C.sub.6-alkyl).sub.2, C.sub.1-C.sub.4-alkoxy, aryl and heteroaryl, where aryl and hetaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy and halogen; ##STR00011## R is C.sub.4-C.sub.24-alkyl or C.sub.4-C.sub.24-alkenyl; and # indicates the point of attachment to the terminus and/or to the polymer backbone of the polymer radical P.

2. The polymer composition as claimed in claim 1, wherein P is a p-valent polymer radical derived from a linear or branched poly-(C.sub.2-C.sub.4-alkylene oxide) polymer.

3. The polymer composition as claimed in claim 1, wherein P is a poly(ethylene oxide), a poly(propylene oxide) or a poly(ethylene oxide-co-propylene oxide).

4. The polymer composition as claimed in claim 1, wherein the number average of p is from 1.8 to 3.

5. The polymer composition as claimed in claim 1, wherein: k is 0; n is 0; and Q is O.

6. The polymer composition as claimed in claim 1, wherein a number average molecular weight of the polymer radical P is from 500 to 50000 Dalton.

7. The polymer composition as claimed in claim 1, wherein R is linear C.sub.4-C.sub.24-alkyl or linear C.sub.4-C.sub.24-alkenyl.

8. The polymer composition as claimed in claim 1, wherein R is C.sub.6-C.sub.18-alkyl or C.sub.6-C.sub.18-alkenyl.

9. The polymer composition as claimed in claim 1, wherein the polymer P1 and the succinic anhydride of the formula (II) are reacted in a relative amount such that the molar ratio of NH.sub.2 groups in the polymer P1 to the anhydride groups of the succinic anhydride of formula (II) is in the range from 1:1 to 1:5.

10. The polymer composition as claimed in claim 1, wherein the polymer P1 is obtained by reacting a polymer of the formula (III):
P-(Q-H).sub.p(III) with a compound of the formulae (V), (VI) or (VII): ##STR00012## wherein p, k, P, Q and R.sup.1 are as defined in claim 1, and R.sup.L is hydrogen or a hydrocarbon radical having 1 to 8 carbon atoms.

11. The polymer composition as claimed in claim 1, further comprising a non-ionic surfactant.

12. The polymer composition as claimed in claim 1, which is in the form of an aqueous solution of the polymer material.

13. The polymer composition as claimed in claim 1, which has a pH in the range from 5.0 to 10.0.

14. A process for the manufacturing of the polymer composition as claimed in claim 1, which comprises reacting the polymer P1 with a succinic anhydride of the formula (II).

15. A viscosity modifier comprising the polymer composition of claim 1.

16. The viscosity modifier of claim 15, wherein the polymer composition is a thickener in a water-borne coating composition.

17. A water-borne coating composition, comprising the polymer composition of claim 1 and a polymer P2 in the form of a polymer latex.

18. The coating composition of claim 17, comprising the polymer composition in such an amount that the polymer material of the polymer composition is from 0.1 to 5% by weight, based on the polymer P2.

19. The coating composition of claim 17, comprising i) 1 to 70% by weight, based on the total weight of the coating composition, of at least one fine particulate solid material, selected from the group consisting of pigments and fillers; ii) 5 to 40% by weight, based on the total weight of the coating composition, of a polymer P2 in the faun of a polymer latex and calculated as solid polymer P2; iii) 0.01 to 3% by weight, based on the total weight of the coating composition, of the polymer composition, calculated as polymer material; and iv) 20 to 93% by weight, based on the total weight of the coating composition, of water.

Description

PREPARATION EXAMPLES

(1) TABLE-US-00001 TABLE 1 Commercially available products that were used as a polymer of the formula (III), a non-ionic surfactant and a polymer P2 in the form of a polymer latex: Name Composition Supplier Pluriol E8000 polyethylene glycol, average BASF SE molecular mass M.sub.N approx. 8000 g/mol; used as polymer of formula (III). Dehydol O4 C8-fatty alcohol ethoxylated with BASF SE 4 EO units; used as non-ionic surfactant. Acronal Plus 4670 Acrylic latex, solid content 49-51% BASF SE by weight, particle size approx. 140 nm; used as polymer P2 in the form of a polymer latex.
Preparation of Polymer P1-a:

(2) A mixture of 80.0 g (0.02 mol of hydroxyl groups) Pluriol E8000, 4.1 g (0.025 mol) isatoic anhydride (IA), and 0.25 g (0.3% by weight) 1,4-diazabicyclol[2.2.2]octan was heated at 80 to 140 C. until no more carbon dioxide was evolved. The obtained product was a solid with an amine number of 15 mg KOH/g.

(3) Preparation of Polymer Compositions Useful as Thickeners

Example 1 (According to the Invention)

(4) A mixture of 41.0 g (0.005 mol) polymer P1-a and 4.0 g (0.015 mol) (2-Dodecen-1-yl)succinic anhydride was heated at 80 C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol 04 and 158 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 2 (According to the Invention)

(5) A mixture of 41.0 g (0.005 mol) polymer P1-a and 4.0 g (0.015 mol) (2-Dodecen-1-yl)-succinic anhydride was heated at 180 C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol 04 and 158 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 3 (According to the Invention)

(6) A mixture of 41.0 g (0.005 mol) polymer P1-a and 6.7 g (0.025 mol) (2-Dodecen-1-yl)-succinic anhydride was heated at 180 C. for 10 hours under nitrogen gas. Afterwards 23 g Dehydol 04 and 165 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 4 (According to the Invention)

(7) A mixture of 41.0 g (0.005 mol) polymer P1-a, 3.4 g (0.015 mol) of (2-Nonen-1-yl)-succinic anhydride was heated at 180 C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol 04 and 154 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 5 (Comparative)

(8) A mixture of 40.0 g (0.005 mol) Pluriol E8000 and 4.0 g (0.015 mol) (2-Dodecen-1-yl)succinic anhydride was heated at 80 C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol 04 and 154 g water were added. The resulting product was a viscous water solution including the obtained modified polyethylene glycol in a concentration of 20% by weight.

Example 6 (Comparative)

(9) First, 44.0 g polymer P1-a was heated at 80 C. and then 22 g Dehydol 04 and 154 g water were added. The resulting product was a viscous water solution with a concentration of 20% by weight.

Example 7 (According to the Invention)

(10) A mixture of 41.0 g (0.005 mol) polymer P1-a, 5.3 g (0.015 mol) Octadecenylsuccinic anhydride was heated at 180 C. for 10 hours under nitrogen gas. Afterwards 23 g Dehydol 04 and 161 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 8 (According to the Invention)

(11) A mixture of 20.0 g (0.005 mol) Pluriol E4000, 80 g Pluriol E8000 (0.01 mol), 6.1 g (0.037 mol) isatoic anhydride (IA), and 0.3 g 1,4-diazabicyclol[2.2.2]octan was heated at 80 to 140 C. until no more carbon dioxide was evolved. Then, the material was cooled down to 80 C. and 20 g (2-Dodecen-1-yl)-succinic anhydride was added. The mixture was kept at 180 C. for 10 hours under nitrogen gas and afterwards 53 g Dehydol 04 and 424 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

(12) Performance Testing

(13) In order to test the thickening effect of the thickeners obtained in examples P1-a and 1 to 8, water-borne coating compositions were prepared by mixing 4.0 g of each of the above thickeners, 26 g water, and 70 g Acronal Plus 4670. The mixtures were homogenized with the laboratory dissolver Dispermat (VMA Getzmann GmbH) at 1500 rpm for 10 minutes and, after a standing time of at least 20 hours, slightly stirred with a wooden spatula. Afterwards the viscosities of the obtained homogenates were measured at shear rates in the range of 0.1 to 10000 sec.sup.1 using the cone-plate viscometer Haake RC20 CPS P with cone C50-1. The results are summarized in Table 2.

(14) TABLE-US-00002 TABLE 2 Rheological behavior of coating compositions Viscosity (mPas) at shear rates [sec.sup.1] of Example 0.1 0.5 1 10 100 1000 10000 P1-a (comparative) 75 40 25 15 15 10 10 1 420 420 420 400 380 230 80 2 550 560 550 530 490 300 120 3 520 520 500 450 410 250 90 4 80 120 150 150 120 90 60 5 (comparative) 60 100 110 100 90 70 50 6 (comparative) 75 40 25 15 15 10 10 7 1500 1450 1200 1000 750 90 40 8 850 840 840 820 780 400 70

(15) It can be seen from Table 2 that all six thickeners of examples 1 to 4, 7, and 8 that are in accordance to the present invention impart substantially higher viscosities to water-borne coating compositions than the comparative thickeners of examples P1-a, 5, and 6 which differs from the thickeners of the examples according to the invention in that it lacks anthranilate groups. As can also be seen from Table 2 this beneficial effect is present in all cases over the broad range of shear rates measured.